Basic hemicyanine dyestuffs

ABSTRACT

Water-soluble basic dyestuffs of the formula   IN WHICH A stands for a benzene or naphthalene radical that may be substituted, ALK represents each a lower alkyl group preferably of one to four carbon atoms, R represents hydrogen or a lower alkyl radical preferably of one to four carbon atoms that may be substituted, Y represents a -CO- or -SO2- group, R1 is an aliphatic, araliphatic, aromatic or heterocyclic radical and X represents an anion, and wherein the benzene nucleus a may further contain non-ionic substituents, which are suitable for the dyeing or printing of textile fibrous materials consisting of native or regenerative cellulose, silk, acetate rayon, acidmodified polyamides or polyesters, polyacrylonitrile or polyvinylidene cyanide or leather.

United States Patent Friedrich et al.

[451 July 25, 1972 [54] BASIC HEMICYANINE DYESTUFFS [72] Inventors: Herbert Friedrich, Offenbach/Main; Gunther Tripp, Frankfurt/Main, both of Germany [21] Appl.No.: 833,198

I30] Foreign Application Priority Data June 20, 1968 Germany ..P i7 69 631.0

[56] References Cited UNITED STATES PATENTS 3,3l 1,619 3/1967 Fisher et al. ..260/240.8

Primary Examiner-Henry R. Jiles Assistant Examiner-G. Thomas Todd Attorney-Curtis, Morris & Safford [57] ABSTRACT Water-soluble basic dyestuffs of the fonnula All: Alk

in which A stands for a benzene or naphthalene radical that may be substituted, ALK represents each a lower alkyl group preferably of one to four carbon atoms, R represents hydrogen or a lower alkyl radical preferably of one to four carbon atoms that may be substituted, Y represents a -CO or SO,- group, R is an aliphatic, araiiphatic, aromatic or heterocyclic radical and X represents an anion, and wherein the benzene nucleus a may further contain non-ionic substituents, which are suitable for the dyeing or printing of textile fibrous materials consisting of native or regenerative cellulose, silk, acetate rayon, acid-modified polyamides or polyesters, polyacrylonitrile or polyvinylidene cyanide or leather.

6 Claims, No Drawings BASIC HEMICYANINE DYESTUFFS The 'present invention relates tobasic dyestuffs free from sulfonic acid groups and having the general formula I Alk an:

Alk Alk in which A and Alk are defined as above, in the presence of an acidic condensing agent, with an amine of the general formula Ill nmQn-xr-m (III) in which Y,R, R and a have the meaning given above.

As l,3,3-trialkylindoline-Z-methylene-w-aldehydes corresponding to formula I] there are used according to the present invention, for example l,3,3-trimethyl-indoline-2- methylene-uraldehyde or l,3,3-triethyl-indoline-Z-methylenew-aldehyde or derivatives thereof substituted in the benzene nucleus A by halogen atoms, alkyl, alkoxy, nitro, cyano or carbalkoxy groups, moreover, l,3,3-trialkyI- LS-benZoindoIine-Z- mthylene-m-aldehydes.

As amines of formula III for example the following are suited: l-amino-4-a'cylaminobenzenes or l-amino-4-(N-alkyl)-acylamino-benzenes where the acyl radical denotes a radical of an aliphatic, araliphatic, aromatic or heterocyclic carboxylic acid radical, moreover l amino-4-alkylsulfonylaminoben2enes, l -amino-4-aralkylsulfonylaminobenzenes, or l-amino-4-aryl-sulfonylamino-benzenes or 1- amino-4-(N-alkyl)-alkylsulfonylamino-benzenes, l-amino-4- (N-alkyl)-aralkylsulfonylamino-benzenes or l-arnino-4-(N-alkyl)-arylsulfonylamino-benzenes; the benzene radical a in the aforesaid amines may carry non-ionic substituents such as halogen atoms, alkyl, alkoxy, nitro, trifluoromethyl, cyano, acyl, acylamino, carboxylic acid amide, sulfone or sulfonic acid amide groups.

The amines of formula in used in the process of the invention can be obtained, for example, by reaction of the corresponding 4-nitro-l-amino-benzenes or 4-nitro-lalkylarnino-benzenes with the corresponding aliphatic,

araliphatic, aromatic or heterocyclic carboxylic acid halides.

5 acetic acid, or aromatic sulfonic acids. The dyestuffs generally. precipitate automatically from the aqueous reaction medium of formula 11] is suitably conducted in an aqueous solution. As acid condensing agents inorganic or organic acids may be used, for example hydrohalic acids, sulfuric acid, nitric acid, phosphoric acid, aliphatic carboxylic acids such as formic or and can be isolated by filtration. Dyestuffs that are readily soluble may be separated from the reaction mixture by salting out or be isolated in form of their souble-salts by addition of zinc or cadmium halides.

The dyestufi's of the invention corresponding to formula 1 contain as anion x the radical of an inorganic or organic acid, for example, of hydrochloric acid, hydrobromic acid or hydroiodic acid, of a metal-hydrohalic acid, sulfuric acid, nitric acid, of a phosphoric acid, formic acid, acetic acid, oxalic acid or of p-toluene-sulfonic acid.

The new dyestuffs are suitable for the dyeing or printing of tannin-treated natural or regenerated cellulose fibers, silk, leather or fully-synthetic fibers such as acetate rayon or acidmodified polyamides or polyesters fibers, especially of fibers, yarns or tissues consisting of polymers or copolymers of acrylonitrile or vinylidene cyanide. In the majority of cases the yellow dyeings produced by the present dyestuffs on these fibers are very clear and deep in shade nd have a very good fastness to light and wet processing.

The dyestuffs are, in general, largely insensitive toward variations of the pH value of the dyebath being thus applicable as well in weakly acidic or strongly acidic bath. Moreover, they are stable at temperatures above 100' C as practised in high-temperature dyeing. Under normal dyeing conditions wool is completely resisted by these dyestuffs.

The following Examples are to illustrate the invention but they are not intended to limit it thereto; the parts and percentages being be weight unless otherwise stated.

EXAMPLE 1 A mixture of 4 parts of 5-amino-2-acetamino-toluene, 10 parts by volume of 5N hydrochloric acid, 10 parts by volume of water and 5 parts of l,3,3-trimethyl-2-methylene-indoline- (ii-aldehyde were heated shortly to the boil. After cooling the batch, the precipitated dyestuff was drawn off, recrystallized from water and dried at 60 C. 7.4 parts of the dyestufi of formula H1O CH:

were obtained soluble in water while giving a yellow color.

Five g of that dyestuff were stirred together with 15 com of a 50 percent acetic acid and dissolved by pouring on the paste 300 com of boiling water. This solution was introduced into a dyeing apparatus into which 6 l of water, 2 g of a condensation product of 30 mols of ethylene oxide with 1 mol of no- .nylphenol and 3 g of crystalline sodium acetate were fed. Then a cross-wound bobbin containing 500 g of an endless yarn made of polyacrylonitrile was placed into the apparatus and in raising gradually the temperature to 100 C the yarn was dyed at the boil for about 1 hour. Then the bath was cooled to about 70 C and the yarn dyeing completed as usual.

A very clear greenish yellow dyeing of excellent fastness to light and wet processing was obtained.

EXAMPLE. 2

A mixture of 5.6 parts of 5-amino-2-benzoylamino-toluene, 10 parts by volume of a percent phosphoric acid, 20 parts by volume of water and 5 parts of l,3,3-trimethyl-2- methylene-indoline-m -aldehyde were heated shortly to the boil. After cooling the bath, the precipitated dyestuff was drawn olf, recrystallized from water and dried at 60 C. 9.5 parts of the dyestufl' of formula HsC CH:

N H (111: a

were obtained soluble in water while giving a yellow color.

One g of this dyestufl' was stirred to a paste with 2.5 g of a 50 percent acetic acid and dissolved in 6 l of water. To this dyebath l g of crystalline sodium acetate and 10 g of calcined sodium sulfate were added. Then 100 g of pre-washed yarn made of polyacrylonitrile staple fiber were introduced into the dyebath being heated to 60 C, then while rising slowly the dyebath temperature to 100 C the yarn was dyed for 1 hour at the boil. Subsequently, the bath was cooled to about 70 C and the yarn rinsed and dried.

A clear, greenish yellow dyeing of excellent fastness to light and wet processing was obtained.

EXAMPLE 3 A mixture of 3.4 parts of -amino-2-(N-methyl)-benzenesulfonylamino-toluene, 5 parts by volume of 5N hydrochloric acid, 15 parts by volume of water and 2.5 parts of 1,3,3- trimethyl-Z-methyIene-indoline-w-aldehyde were heated shortly to the boil. After cooling the batch, the precipitated dyestuff was suction-filtered, recrystallized from water and dried at 60 C. 5.2 parts of the dyestufi of formula were obtained soluble in water while giving a yellow color.

One g of the dyestufi' obtained was stirred into a paste with 2 g of a 50 percent acetic acid and dissolved in 5 l of water. Furthermore to the dyebath l g of crystalline sodium acetate was added. Then 100 g of a pre-washed tissue made of acidmodified polyester fiber were introduced therein at 60 C and while raising gradually the temperature of the bath the tissue was dyed during 1 hour at 1 C. Subsequently, the bath was cooled to about 70 C and the yarn rinsed and dried. A greenish yellow dyeing was obtained having a good fastness to light and wet processing.

The following Table lists further dyestuffs which correspond to formula la that are obtained according to the process of the present invention as well as the shades produced by said dyestuffs on polyacrylonitrile fibers Ag /Alk o-cH=oH-NH N Y-m x g/ a a in. (Ia) Substituent Alk Z in a R Y R, X shade CH, H H CO CH, Cl Yellowish orange CH, 3-Cl H CO CH, Cl reddish yellow CH, 3,5-Cl, H CO CH, Cl greenish yellow CH, H 2-0C,H, H CO CH, Cl CH 3-OCH, H CO CH, Cl yellowtinged organge CH, H 2,5 CO CH, Cl reddish (OCH,), orange CH, H 3-CH, CO CH, H,PO, greenish yellow CH, H 3,5 H CO CH, H,PO,

s): CH, H 2,3 H CO CH, Cl yellow CH, H CH, CH, Cl CH, H C,H, CO CH, Cl greenish yellow CH, H 3 -C,H,OOCCH, m CH, Cl yellow -CN CH, CH, --CH,CI Cl CH, H CH, H Cl CH, H H SO, CH, Cl greenish yellow CH, H 3-Cl H 80, CH, Cl CH, H 3-OCH, H SO, CH, Cl CH, H 3-CH, H S0, CH, Cl CH, H 2,3 H So, CH, H,P0, s):

CH, H CH, CH, Cl

cmn H so can 300K C O O CH, H 3-OCH, H CO C,H, Cl yellow CH, 2,5(0CH,), H CO 0,", Cl reddish yellow CH, H 2,5(0C,H,), H CO CH, Cl golden yellow CH, H 3-Cl H CO C,H, H,P0, greenish yellow CH, H 3-CH, H CO C,H, Cl

CH, H 2-OCH, H CO C,H, Cl yellow -5-CH, CH, H CH, C,H, Cl greenish yellow CH, H H CO --C,H,CH, H,P0,

-4 CH, H 3-OCH, CO C,H,CH, Cl yellow -4 CH, H 3-CH, H CO C,H,CH, H,PO, greenish -4 yellow CH, H CH, CO :CJ-LCH, H,PO, CH, H CO C,H,0CH, Cl yellow -4 CH, H H CO C,H,0H H,P0, greenish -2 yellow CH, 3-CH, H 00 -c,n,on H,P0,

-2 CH, 3,5 H CO C,H, H,P0, yellow s): CH, H 3-CH, H CO --C,H,N(CH,),-4 reddish yellow H J 4 CH, H H CO -C,H,N(CH,),-4

H 4 CH, H SO, C,H, greenish yellow CH, H 3-0CH, H S0, C,H, Cl CH, H 3-CH, H S0, C,H, Cl CH, H 3,5 H 80, C,H, H,PO,

s)s CH, H 2,3 H S0, C,H, H,PO,

a): CH, CH, 80, C,H, Cl CH, CH, S0, C,H, Cl CH, C,H, S0, C,H, Cl

CH, H 3-CH, CH, SO, C,H, H,PO, greenish yellow CH, H 3-0CH, CH, SO, C,H, Cl greenish yellow CH, 3-CH, H CO CH, HSO, yellow CH, 3-CH, H CO CH, NO, CH, 3-CH, H CO CH, H,CO0 CH, H 3-OCH, H CO CH,C,H, H,P0, CH, H 3-OCH, H CO Pyridino H,PO,

We claim:

the general formula 3. The basic dyestuff of the formula .Alk All:

l 4. The basic dyestuff of the formula Alk in which Z represents hydrogen, chlorine, lower alkyl, lower 7 alkoxy or carbo-low er alkoxy Alk represents each lower al- The 9 dyestuff ofthe formula H CH3 kyl, R represents hydrogen or lower alkyl, Y represents m @11 5 ggga i fi ff f l CO- or --SO;, R, represents lower alkyl, chloromethyl,

Ha C Ha N CH:

benzyl, phenyl, lower alkyl-phenyl, lower alkoxy-phenylf i hydroxyphenyl, di-(lower alkyl)-amino-phenyl or pyridinyl, P and 0 each represent hydrogen, chlorine, lower alkyl, lower 50 alkoxy cyano, or lower alkylsulfone, and 1& represents an anion. w

2. The basic dyestuff of the formula H30 CH3 COH=CHNH NH-C-C'Hs 01 63/ l N H: (EH3 

2. The basic dyestuff of the formula
 3. The basic dyestuff of the formula
 4. The basic dyestuff of the formula
 5. The basic dyestuff of the formula
 6. The basic dyestuff of the formula 